EP3774027B1 - Électro-catalyseurs, leur préparation,et leur utilisation pour la synthèse de l'ammoniac - Google Patents

Électro-catalyseurs, leur préparation,et leur utilisation pour la synthèse de l'ammoniac Download PDF

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Publication number
EP3774027B1
EP3774027B1 EP19781678.8A EP19781678A EP3774027B1 EP 3774027 B1 EP3774027 B1 EP 3774027B1 EP 19781678 A EP19781678 A EP 19781678A EP 3774027 B1 EP3774027 B1 EP 3774027B1
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Prior art keywords
ammonia
cathode
metal component
nitrogen
anode
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German (de)
English (en)
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EP3774027A1 (fr
EP3774027A4 (fr
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Alex Schechter
Manjunatha Revanasiddappa
Valentina GOLDSHTEIN
Aleksandar KARAJIC
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Ariel Scientific Innovations Ltd
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Ariel Scientific Innovations Ltd
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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Definitions

  • the present invention in some embodiments thereof, relates to metal based catalysts and uses thereof for, e.g., ammonia synthesis.
  • the ammonia is extensively produced by using Haber-Bosch process developed in nineteenth century which requires very high pressure and temperature. Industries produce annually more than 200 million tons of ammonia from this method and majority of it used for production of fertilizers.
  • the hydrogen required for this process is generated from steam regeneration, which consumes three to five percent of total natural gas production and releases huge quantity of greenhouse carbon dioxide gas to atmosphere.
  • WO 2011/089522 A2 describes catalyst compositions comprising a core-shell structure, the core contains Pt, a Pt alloy, Ru, Re, Pd or Ir, while the shell comprises one or more layers of a precious metal, e.g., Pt or Ir, and alloys thereof that can include one or more other precious metals, e.g. Ru, Re, and Pd, and optionally one or more transition metals, e.g. Mo, Co and Cr.
  • WO 01/54216 A2 discloses nanosized powders of Pt and alloys, coated with catalytically active metals such as Pt, Pd, Ru, Re, Ir, Au, Ag, Co, Fe, Ni, Y, and Mn.
  • US 2006/134505 A1 discloses Pd or Pd alloy nanoparticle catalysts coated with main group transition metals, and bound to carbon black whereby the resulting material is used in a cathode of an electrochemical cell.
  • US 2012/308467 A1 describes catalytic synthesis of ammonia using core-shell iron-iron oxide nanoparticles.
  • a composition comprising a first metal component and a second metal component characterized by a molar ratio of said first metal component to said second metal component is in the range of 1:9 to 9:1, wherein: (i) at least one surface of said second metal component is coated with said first metal component; (ii) first metal component comprises Fe 2 O 3 or Fe 3 O 4 or Fe 2 O 3 FeO and wherein said second metal component comprises TiO 2 , and (iii) said composition is in the form of particles.
  • the particles have a size in the range of 1 nm to 50 ⁇ m.
  • the composition further comprises a substrate, wherein the first metal component and the second metal component are deposited on at least one surface of the substrate.
  • the substrate is selected from the group consisting of: carbon black, activated carbon, graphite, carbon nanotube, and any combination thereof.
  • the carbon black is selected from the group consisting of: carbon nanotube, graphene, Vulcan XC-72, Black Pearls 700, Black Pearls 800, Vulcan XC-605, Regal 350, Regal 250, Black Pearls 570, and Vulcan XC-68.
  • the carbon black is Vulcan XC-72.
  • the substrate is present at a concentration of 5% to 50%, by total weight of the composition.
  • the composition is a catalyst.
  • the composition is for use in electrochemical ammonia synthesis.
  • an electrochemical cell comprising the catalyst of the present invention, wherein the catalyst is a cathode.
  • the electrochemical cell further comprises an electrolysis cell container comprising an inlet and an outlet; a distributor, wherein the distributor is in fluid communication with the cathode and the inlet; and an anode, wherein: (i) the anode and cathode are spaced apart from each other inside the container; (ii) the anode is in electrical communication with the cathode; (iii) the largest dimension of the anode and the cathode is defined by transverse cross-section dimensions of the electrolysis cell container; and (iv) the cathode is at least 50 fold thicker than the anode.
  • the container is configured to allow a nitrogen gas to enter through the inlet and to contact the distributor.
  • the distributor is configured to uniformly distribute the gas over a surface of the cathode.
  • the cathode, the anode or both is at least partially porous.
  • the container is configured to allow a nitrogen gas to enter thereto and to contact the cathode.
  • the electrochemical cell is configured to electrically connect an electric potential to the anode and to the cathode.
  • the electrochemical cell is configured to synthesize ammonia at a rate of 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 at 1 atm N 2 .
  • the electrochemical cell is configured to synthesize ammonia at a rate of at least 1 ⁇ 10 -9 mol cm -2 s -1 on the catalyst at 1 atm N 2 .
  • the electrochemical cell is further configured to synthesize hydrogen.
  • the anode is dimensioned to curb production of hydrogen.
  • the remaining gas is directed via the outlet into a collecting chamber.
  • the collecting chamber is an acid trap.
  • the anode comprises comprise nickel, iron, zinc, cobalt, chromium, titanium, or any oxide or a combination thereof.
  • the container further comprises an alkaline electrolyte solution.
  • the electrolyte solution is saturated with nitrogen.
  • the alkaline electrolyte solution is a sodium hydroxide (NaOH) solution, potassium hydroxide (KOH) solution or lithium hydroxide (LiOH) solution.
  • the alkali electrolyte solution is present at a concentration of 0.1 to 5 M.
  • a process of synthesizing ammonia comprising: (i) contacting a nitrogen gas with the cathode of the electrochemical cell of the present invention, and (ii) applying an electric potential to the anode and the cathode, thereby obtaining the ammonia.
  • the synthesis is performed at a temperature of from 20 °C to 80 °C.
  • the temperature is in the range of from 20 °C to 60 °C.
  • the synthesis is characterized by a faradaic efficiency in the range of 1% to 30%.
  • the rate of ammonia production is in the range of 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 .
  • the present invention in some embodiments thereof, relates to catalysts comprising a first metal component and a second metal component, and uses thereof for nitrogen reduction, e.g., for the electrochemical synthesis of ammonia at ambient temperature and pressure, by using water and pure nitrogen gas or air.
  • the present invention relates to a composition comprising one or more metal elements.
  • the present invention relates to a composition comprising a bimetallic catalyst.
  • the composition comprises two or more catalytically active components.
  • the catalytically active components induce a synergistic effect on each other.
  • the composition has high electrocatalytic activity towards nitrogen reduction.
  • the electrocatalytic nitrogen reduction is carried out at ambient pressure and temperature in aqueous media by using either air or pure nitrogen as nitrogen sources.
  • a composition comprising a first metal component and a second metal component characterized by a molar ratio of said first metal component to said second metal component is in the range of 1:9 to 9:1, wherein: (i) at least one surface of said second metal component is coated with said first metal component; (ii) first metal component comprises Fe2O3 or Fe3O4 or Fe2O3FeO and wherein said second metal component comprises TiO2, and (iii) said composition is in the form of particles.
  • the composition comprises a first metal component comprising one or more metals alloying with a second metal component comprising one or more metals.
  • the molar ratio of the first metal component to the second metal component are in the range of 1:9 to 9:1, 2:9 to 9:1, 3:9 to 9:1, 4:9 to 9:1, 5:9 to 9:1, 6:9 to 9:1, 7:9 to 9:1, 8:9 to 9:1, 9:9 to 9:1, 1:9 to 9:2, 1:9 to 9:3, 1:9 to 9:4, 1:9 to 9:5, 1:9 to 9:6, 1:9 to 9:7, 1:9 to 9:8, or 1:9 to 9:9, including any range therebetween.
  • the particles have a size in the range of 1 nm to 50 ⁇ m, 3 nm to 50 ⁇ m, 5 nm to 50 ⁇ m, 10 nm to 50 ⁇ m, 25 nm to 50 ⁇ m, 50 nm to 50 ⁇ m, 100 nm to 50 ⁇ m, 250 nm to 50 ⁇ m, 500 nm to 50 ⁇ m, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 500 nm, 1 nm to 250 nm, or 1 nm to 100 nm, including any range therebetween.
  • the first metal component and/or second metal component comprise two metals.
  • the first metal component comprises Ru, Pt, Pd, Sn, Co, Mo, and any combination thereof.
  • the second metal component comprises Sn, Ru, Fe, Pt, Pb, Bi, Hg, Cd, and any combination thereof.
  • the first metal component comprises the active metal.
  • the second metal component comprises a co-catalyst.
  • co-catalysts include Sn, Pb, Bi, Hg, Cd, and their corresponding oxides, sulfides, selenides, nitrides, and phosphides.
  • a composition as described herein is for use in electrochemical ammonia synthesis.
  • the second metal component improves the activity of the first metal component.
  • a composition comprising a second metal component also referred to as "co-catalyst"
  • has a higher ammonia production when compared to the corresponding composition without the second metal component.
  • ammonia production using a composition according to the present invention comprising a second metal component is at least 1 fold, at least 2 fold, at least 5 fold, at least 10 fold, at least 12 fold, at least 50 fold, or at least 100 fold, higher then when using the corresponding composition without the second metal component.
  • second metal component is not consumed in the process.
  • the second metal component prevents hydrogen evolution during electrochemical ammonia synthesis. In some embodiments, the second metal component prevents the formation of hydrogen next to the first metal component.
  • a composition comprising Fe 2 O 3 , Fe 3 O 4 or Fe 2 O 3 FeO and TiO 2 .
  • the composition comprises Fe 2 O 3 , Fe 3 O 4 or Fe 2 O 3 FeO as the first metal component and TiO 2 as the second metal component, in a molar ratio in the range of 1:9 to 9:1.
  • the first metal component is Fe and the second metal component is Sn, in a molar ratio in the range of 1:9 to 9:1.
  • the first metal component is Ru or Fe and the second metal component is Pt or Pd or Sn, in a molar ratio in the range of 1:9 to 9:1.
  • the first metal component is Pt and the second metal component is Ru in a molar ratio in the range of 1:9 to 9:1.
  • composition comprising Ruthenium (Ru) and Platinum (Pt), wherein the molar ratio of the Ru to the Pt is in the range of 1:10 to 10:1, respectively.
  • the Ru:Pt molar ratio is in the range of 1:10 to 9:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:9 to 9:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:8 to 8:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:7 to 7:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:6 to 6:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:5 to 5:1, respectively.
  • the Ru:Pt molar ratio is in the range of 1:4 to 4:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:3 to 3:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is in the range of 1:2 to 2:1, respectively. In some unclaimed embodiments, the Ru:Pt molar ratio is 1:1, respectively.
  • the Ru:Pt molar ratio is 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, respectively, including any value and range therebetween.
  • the molar ratio of the Ru to the Pt is about 1:1 ( ⁇ 20%).
  • the composition is in the form of a core-shell structure in which the core particle comprises metal particles covered with the outer layer comprising a metal or an alloy thereof. In some embodiments, the composition is in the form of a core-shell structure in which the core particle comprises a first metal component particles covered with the outer layer comprising a second metal component as described herein.
  • the composition is in the form of a core-shell structure in which the core particle comprises metal particles covered with the outer layer comprising a metal or an alloy thereof.
  • the term "shell” refers to the coating domain surrounding the core.
  • coated by a shell it is meant to refer to a composition of two or more entities, namely an entity that defines an enclosure (the enclosing entity, i.e. the shell) and the entity (or entities) that is being at least partially enclosed therein.
  • the coating may be conformal with the exact contour of the core.
  • the core comprises or is made of a plurality of particles.
  • Particle(s) coated by a shell may be characterized by a discrete inner and outer surface wherein the inner surface constitutes the boundary of the enclosed area or space.
  • the enclosed area or space may be secluded from the exterior area of space which is bounded only by the outer surface.
  • the closure of the enclosing entity may depend of the size, shape and chemical composition of the entity that is being enclosed therein, such that the enclosing entity may be "closed” for one entity and at the same time be “open” for another entity.
  • structures presented herein are closed with respect to certain chemical entities which cannot pass through their enclosing shell, while the same "closed" structures are not closed with respect to other entities.
  • alloy refers to a monophasic or polyphasic metallic material of a binary or polynary system.
  • the starting components may enter into metallurgical interactions with one another and thereby lead to the formation of new phases (e.g., mixed crystals, intermetallic compounds, superlattice).
  • the alloy can include deposition of two or more target materials, so as to form a di-segmented nanostructure (e.g., if two or more target metals are deposited sequentially), a tri-segmented nanostructure (e.g., if three or more target metals are deposited sequentially), etc. At least one of the deposited metals may be etched at later stages of the process. The process can include deposition of one or more such materials.
  • deposited on at least one surface is also referred to herein, for simplicity, as a coating on substrate, or surface of a substrate.
  • the term "coating”, or any grammatical derivative thereof is defined as a coating that (i) is positioned above the substrate, (ii) is not necessarily in contact with the substrate, that is to say one or more intermediate coatings may be arranged between the substrate and the coating in question (however, it may be in contact with the substrate), and (iii) does not necessarily completely cover the substrate.
  • the composition further comprises a substrate.
  • a first metal component and a second metal component are deposited on at least one surface of the substrate.
  • the substrate comprises carbon
  • the substrate comprises a co-catalyst.
  • a co-catalyst is a substrate to the active material and helps hindering the competing hydrogen reduction reaction.
  • Substrate usable according to some embodiments of the present invention can have, for example, organic or inorganic surfaces.
  • the substrate is selected from, but is not limited to, carbon, a metal oxide, a polymer, or any combination thereof.
  • Non-limiting exemplary substrates are selected from activated carbon, graphite, carbon nanotube, metal mesh or foam, Ni foam, Sn foam, or woven, ceramic materials, Toray paper, carbon cloth, carbon paper, or any combination thereof.
  • Non-limiting exemplary carbon is selected from carbon black, activated carbon, graphite, carbon nanotube, and any combination thereof.
  • the carbon black may be selected from, without being limited thereto, carbon nanotube, graphene, Vulcan XC-72, Black Pearls 700, Black Pearls 800, Vulcan XC-605, Regal 350, Regal 250, Black Pearls 570, and Vulcan XC-68, or any combination thereof.
  • the carbon comprises Vulcan XC-72.
  • the composition described herein is identified for use as a catalyst or as an electro-catalyst.
  • the catalyst is a cathode.
  • the substrate is present at a concentration of 2% to 50%, by total weight of the composition. In some embodiments, the substrate is present at a concentration of 2% to 30%, by total weight of the composition. In some embodiments, the substrate is present at a concentration of 3% to 25%, by total weight of the composition. In some embodiments, the substrate is present at a concentration of 4% to 20%, by total weight of the composition. In some embodiments, the substrate is present at a concentration of 5% to 15%, by total weight of the composition.
  • the substrate is present at a concentration of 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%, by total weight of the composition, including any value and range therebetween.
  • the substrate is present at a concentration of about 10%, by total weight of the composition.
  • Figure 2B presents a schematic illustration of an apparatus containing electrochemical cell used for nitrogen reduction reaction.
  • the apparatus 100 may be used for synthesizing ammonia by using an alkali electrolyte.
  • the apparatus 100 may be used for synthesizing hydrogen.
  • Apparatus 100 may have a chamber or a container 105 configured to contain the alkali electrolyte.
  • Apparatus 100 may have a working electrode (e.g., a cathode) 110 and an anode 120.
  • Working electrode 110 and anode 120 may be disposed separately from each other in chamber 105.
  • ammonia may be synthesized at an interface of cathode 110.
  • Apparatus 100 may have an electrode separation membrane 125. Electrode separation membrane 125 may be disposed in chamber 105. Electrode separation membrane 125 may be disposed in chamber 105 between cathode 110 and anode 120 and may electrically separate cathode 110 and anode 120, e.g., by dividing chamber 105 to do define a cathode zone 112 and an anode zone 114.
  • Non-limiting exemplary working electrodes 110 e.g., cathode
  • Non-limiting exemplary anodes 120 comprise nickel (Ni), iron, zinc, cobalt, chromium, titanium, or any oxide or a combination thereof.
  • Chamber 105 may have a nitrogen inlet 130 (also referred to as "first nitrogen inlet”).
  • Inlet 130 may be located at a lower part of the chamber 105 e.g., in cathode zone 112.
  • Nitrogen inlet 130 may include a pipe of various shapes and sizes, connected to, attached to, or integrally formed with chamber 105.
  • Nitrogen inlet 130 may allow gas (e.g., nitrogen) to enter chamber 105.
  • the gas (nitrogen) may be humidified with water vapor.
  • Apparatus 100 may be connected to a nitrogen supply unit 150 allowing to supply nitrogen via nitrogen inlet 130.
  • Nitrogen gas may enter nitrogen supply unit 150, and, optionally, the nitrogen may be humidified in nitrogen supply unit 150.
  • Apparatus 100 may have an ammonia outlet 160.
  • Ammonia outlet 160 may be located in chamber 105, e.g., in cathode zone 112. Ammonia outlet 160 may allow ammonia exit chamber 105. Ammonia outlet 160 may further allow hydrogen gas generated to exit chamber 105. Ammonia outlet 160 may further allow other gasses involved in the ammonia synthesis, e.g., nitrogen or water, to exit chamber 105.
  • Apparatus 100 may have an ammonia trap 170.
  • Ammonia trap 170 may be in the form of a container configure to contain an acid (e.g., sulfonic acid).
  • Ammonia trap 170 may have an inlet 180, allowing a gas (e.g., ammonia and other gasses) exiting ammonia outlet 160 to enter ammonia trap 170.
  • Ammonia trap 170 may have a first outlet 190 allowing ammonia exit therefrom.
  • First outlet 190 may be located at a lower part of ammonia trap 170.
  • First outlet 190 may include a valve allowing to control the rate of ammonia flow exiting outlet 190.
  • Ammonia trap 170 may have a second outlet 200 allowing gasses (e.g., nitrogen and hydrogen) to exit therefrom.
  • Outlet 190 may be located at an upper part of ammonia trap 170.
  • Chamber 105 may have another nitrogen inlet 210 (also referred to as "second nitrogen inlet”).
  • Inlet 210 may be located at a lower part of the chamber 105 e.g., in anode zone 114.
  • Nitrogen inlet 210 may include a pipe of various shapes and sizes, connected to, attached to, or integrally formed with chamber 105.
  • Nitrogen inlet 130 may further allow gasses (e.g., nitrogen) exiting second outlet 200 to reenter, or recirculate to, chamber 105.
  • Apparatus 100 may have a gas outlet 220.
  • Gas outlet 220 may be located in chamber 105, e.g., in anode zone 114.
  • Gas outlet 220 may allow gasses (e.g., gasses involved in the ammonia synthesis, such as nitrogen or water) exit chamber 105.
  • Gas outlet 220 may include a pipe of various shapes and sizes, connected to, attached to, or integrally formed with chamber 105.
  • gasses exiting chamber 105 via gas outlet 220 may be allowed to reenter, or recirculate, to chamber 105 via nitrogen inlet 130.
  • apparatus 100 is configured to synthesize ammonia at a rate (in mol cm -2 s -1 ) of 1 ⁇ 10 -8 , at least 5 ⁇ 10 -8 , at least 1 ⁇ 10 -9 , 2 ⁇ 10 -9 , at least 3 ⁇ 10 -9 , 4 ⁇ 10 -9 , at least 5 ⁇ 10 -9 , including any value and range therebetween, e.g., at 1 atm N 2 .
  • apparatus 100 is configured to synthesize ammonia at a rate (in mol cm -2 s -1 ) of 1 ⁇ 10 -8 , at least 5 ⁇ 10 -8 , at least 1 ⁇ 10 -9 , 2 ⁇ 10 -9 , at least 3 ⁇ 10 -9 , 4 ⁇ 10 -9 , at least 5 ⁇ 10 -9 , including any value and range therebetween, e.g., at 1 atm N 2 .
  • the apparatus 200 comprises an electrolysis cell container 202 comprising an inlet 210 and an outlet 220, a cathode 206, a distributor 208 in fluid communication with the cathode 206 and the inlet 210, and an anode 204.
  • the anode 204 and cathode 206 are spaced apart from each other inside the container 202. In some embodiments, the anode 204 is in electrical communication 222 with the cathode 206.
  • the surface area of the anode 204 and the cathode 206 is limited, and therefore determined, by wallis of the electrochemical cell and hence the cross-section of the electrolysis cell container 202.
  • the largest dimension of the anode 204 and the cathode 206 is therefore defined by transverse cross-section dimensions of the electrolysis cell container 202.
  • the cathode 206 is at least 50 fold thicker than the anode 204. In some embodiments, the cathode 206 is at least 60 fold, at least 65 fold, at least 70 fold, at least 75 fold, at least 80 fold, at least 85 fold, at least 90 fold, at least 95 fold, at least 100 fold, at least 110 fold, at least 120 fold, or at least 150 fold, thicker than the anode 204.
  • the container 202 of the electrochemical cell 200 is configured to allow a nitrogen gas to enter through the inlet 210 and to contact the distributor 208.
  • the inlet 210 is located across a container wall on the cathode side of the apparatus facing the distributor 208 e.g., in cathode 206 zone.
  • the distributor 208 is disposed between inlet 210 and cathode 206.
  • the inlet 210 may include a pipe of various shapes and sizes, connected to, attached to, or integrally formed with container 202.
  • the inlet 210 allows gas (e.g., nitrogen) to enter the container 202, where it comes into contact (e.g., enters) with distributor 208 and is uniformly distributed over a surface of the cathode 206.
  • the cathode 206 is at least partially porous and gas exiting distributor 208 is uniformly distributed throughout cathode 206.
  • the gas (nitrogen) may be humidified with water vapor.
  • the cathode 206 is at least partially porous.
  • the distributor 208 is configured to uniformly distribute incoming gas and/or gas containing solution.
  • distributor 208 may be made of a porous material, comprise a sieve or have a structure similar to that of a showerhead, or the like and is positioned in contact with or in close proximity to the cathode 206, and pressing the same, in order to allow gas distribution within cathode 206.
  • the distributor 208 is configured to uniformly distribute the gas or gas containing solution over the surface of the cathode 206.
  • the anode 204 comprises an at least partially porous material, and is configured to allow for an electrolyte solution 230 to go through. In some embodiments, the anode 204 is dipped in the electrolyte solution 230.
  • Non-limiting exemplary anodes 204 comprise nickel (Ni), iron, zinc, cobalt, chromium, titanium, or any oxide or a combination thereof.
  • anode 204 in the process of nitrogen reduction reaction, there is a hydrogen evolution competing reaction.
  • the anode 204 is dimensioned to curb production of hydrogen.
  • anode 204 is capable of oxidizing hydrogen.
  • Anode 204 captures the formed hydrogen that can used, saving energy of the total process.
  • the anode 204 avoids the over-generation of hydrogen.
  • the apparatus 200 has an outlet 220.
  • the outlet 220 supports flow of gas.
  • the outlet 220 is an outlet for the ammonia formed during a nitrogen reduction reaction process.
  • the outlet 220 may be located in the container 202, facing the anode 204.
  • the outlet 220 is configured to provide a pathway for hydrogen gas generated in the process as well as other gasses involved in the ammonia synthesis, e.g., nitrogen or water, to exit container 202.
  • the apparatus 200 comprises a collecting chamber 240.
  • the collecting chamber 240 comprises an acid trap.
  • Collecting chamber 240 may be in the form of a container configured to contain an acid (e.g., sulfonic acid).
  • Collecting chamber 240 comprises an inlet 242, through which gas (e.g., ammonia and other gasses) exiting via outlet 220 enters collecting chamber 240.
  • the apparatus 200 can work with minimal quantity of electrolyte 230. Since ammonia dissolves in aqueous solution, the electrochemically generated ammonia saturates quickly in electrolyte 230 and comes out from the cell through outlet 220 and is collected in the collecting chamber 240.
  • apparatus 200 is configured to synthesize ammonia at a rate (in mol cm -2 s -1 ) of 1 ⁇ 10 -8 to 5 ⁇ 10 -9 .
  • apparatus 200 is configured to synthesize ammonia at a rate (in mol cm -2 s -1 ) of 1 ⁇ 10 -8 to 5 ⁇ 10 -9 .
  • Apparatus 100 and apparatus 200 may have various components of the apparatus disclosed herein, such as any of the valves, sensors, weirs, blowers, fans, dampers, or pumps, etc.
  • Operation of the gas rate in the inlet, outlet and the pipes, and the recirculation rates may be controlled by a control unit assisted by the valves, sensors, weirs, blowers, fans, dampers, or pumps, etc.
  • each component of the apparatus is selected to be sufficient, for a given desired fluidization and to provide sufficient contact time to provide e.g., a desired level of water/nitrogen consumption and/or ammonia regeneration.
  • Conditions may be monitored using any suitable type monitoring devices e.g., a computer-implemented system.
  • Variables that may be tracked include, without limitation, pH, temperature, electric potential, conductivity, turbidity, rate of the gas flow in each inlet or outlet, concentration of the alkali solution. These variables may be recorded throughout apparatus 100 and apparatus 200.
  • a monitoring device may also be used to monitor, control and/or automate the operation of the various components of the systems disclosed herein, such as any of the valves, sensors, weirs, blowers, fans, dampers, pumps, etc.
  • the present invention may be a system, a method, and/or a computer program product.
  • the computer program product may comprise a computer-readable storage medium.
  • the computer-readable storage medium may have program code embodied therewith.
  • the computer readable storage medium can be a tangible device that can retain and store instructions for use by an instruction execution device.
  • the computer readable storage medium may be, for example, but is not limited to, an electronic storage device, a magnetic storage device, an optical storage device, an electromagnetic storage device, a semiconductor storage device, or any suitable combination of the foregoing.
  • a non-exhaustive list of more specific examples of the computer readable storage medium includes the following: a portable computer disk, a hard disk, a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or Flash memory), a static random access memory (SRAM), a portable compact disc read-only memory (CD-ROM), a digital versatile disk (DVD), a memory stick, a mechanically encoded device such as punch-cards or raised structures in a groove having instructions recorded thereon, and any suitable combination of the foregoing.
  • RAM random access memory
  • ROM read-only memory
  • EPROM or Flash memory erasable programmable read-only memory
  • SRAM static random access memory
  • CD-ROM compact disc read-only memory
  • DVD digital versatile disk
  • a memory stick a mechanically encoded device such as punch-cards or raised structures in a groove having instructions recorded thereon, and any suitable combination of the foregoing.
  • a computer readable storage medium is not to be construed as being transitory signals per se, such as radio waves or other freely propagating electromagnetic waves, electromagnetic waves propagating through a waveguide or other transmission media (e.g., light pulses passing through a fiber-optic cable), or electrical signals transmitted through a wire.
  • Computer readable program instructions described herein can be downloaded to respective computing/processing devices from a computer readable storage medium or to an external computer or external storage device via a network, for example, the Internet, a local area network, a wide area network and/or a wireless network.
  • the network may comprise copper transmission cables, optical transmission fibers, wireless transmission, routers, firewalls, switches, gateway computers and/or edge servers.
  • a network adapter card or network interface in each computing/processing device receives computer readable program instructions from the network and forwards the computer readable program instructions for storage in a computer readable storage medium within the respective computing/processing device.
  • Computer readable program instructions for carrying out operations of the present invention may be assembler instructions, instruction-set-architecture (ISA) instructions, machine instructions, machine dependent instructions, microcode, firmware instructions, state-setting data, or either source code or object code written in any combination of one or more programming languages, including an object oriented programming language such as Java, Smalltalk, C++ or the like, and conventional procedural programming languages, such as the "C" programming language or similar programming languages.
  • the computer readable program instructions may execute entirely on the user's computer, partly on the user's computer, as a stand-alone software package, partly on the user's computer and partly on a remote computer or entirely on the remote computer or server.
  • the remote computer may be connected to the user's computer through any type of network, including a local area network (LAN) or a wide area network (WAN), or the connection may be made to an external computer (for example, through the Internet using an Internet Service Provider).
  • electronic circuitry including, for example, programmable logic circuitry, field-programmable gate arrays (FPGA), or programmable logic arrays (PLA) may execute the computer readable program instructions by utilizing state information of the computer readable program instructions to personalize the electronic circuitry, in order to perform aspects of the present invention.
  • an electrolysis cell having an electrocatalyst comprising the disclosed composition in an embodiment thereof.
  • the electrocatalyst is the cathode.
  • the term "electrocatalyst” refers a specific form of a catalyst that functions at electrode surfaces or, in some embodiments, may be the electrode surface itself.
  • electrochemical cell refers generally to a device that converts chemical energy into electrical energy, or electrical energy into chemical energy.
  • electrochemical cells have two or more electrodes and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes.
  • electrochemical cells include, but are not limited to, batteries and electrolysis systems.
  • the electrochemical cell is configured to synthesize ammonia at a rate of 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 at 1 atm N 2 .
  • the electrochemical cell is configured to synthesize ammonia at a rate of 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 5 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 10 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 1 ⁇ 10 -10 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 10 ⁇ 10 -10 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , or 1 ⁇ 10 -10 mol s -1 cm -2 to 1 ⁇ 10 -8 mol s -1 cm -2 , or 1 ⁇
  • the electrochemical cell is configured to synthesize hydrogen.
  • the nitrogen reduction reaction is performed in an alkaline electrolyte solution.
  • the solution refers to an aqueous solution.
  • the solution refers to a non-alkaline solution.
  • Non-limiting examples of non-alkaline solutions according to the present invention include Na 2 SO 4 , NaCl, KCl, KBr, KnO 3 , NaNO 3 , NaClO 4 KClO 4 , and KH 2 PO 4 .
  • the alkali aqueous solution refers that the aqueous solution is basic, and, as used herein, the alkali aqueous solution denotes a hydroxide of an alkali metal or an alkali earth metal element.
  • the alkaline electrolyte solution is in the pH value of at least pH 11. In some embodiments, the alkaline electrolyte solution is in the pH value of at least pH 12. In some embodiments, the alkaline electrolyte solution is in the pH value of at least pH 13. In some embodiments, the alkaline electrolyte solution comprises a sodium hydroxide (NaOH) solution. In some embodiments, the alkaline electrolyte solution comprises a potassium hydroxide (KOH) solution. In some embodiments, the alkaline electrolyte solution comprises a lithium hydroxide (LiOH) solution. In some embodiments, the alkaline electrolyte concentration is in the range of 0.001M to 5M.
  • the alkaline electrolyte concentration is in the range of 0.01M to 3M. In some embodiments, the alkaline electrolyte concentration is in the range of 0.05M to 1M. In some embodiments, the alkaline electrolyte concentration is in the range of 0.05M to 0.5M.
  • the alkaline electrolyte concentration is in the range of 0.5M to 3.5M. In some embodiments, the alkaline electrolyte concentration is approximately 3M.
  • ammonia may be synthesized by using the electrolytic cell disclosed herein.
  • a process of synthesizing ammonia comprising: (i) contacting a humidified nitrogen gas with the cathode of the electrochemical cell disclosed herein in any embodiment thereof, and (ii) applying an electric potential to the anode and the cathode, thereby obtaining the ammonia.
  • the ammonia is synthesized by using an alkali solution as described above, according to an embodiment.
  • the ammonia is synthesized by using an aqueous solution.
  • the solution refers to a non-alkaline solution.
  • Non-limiting examples of non-alkaline solutions according to the present invention include Na 2 SO 4 , NaCl, KCl, KBr, KnO 3 , NaNO 3 , NaClO 4 KClO 4 , and KH 2 PO 4 .
  • the synthesis of the ammonia is performed at a temperature of from 10 °C to 80 °C, 20 to 80 °C, 10 °C to 70 °C, 20 °C to 70 °C, 30 °C to 80 °C, 30 °C to 70 °C 30 °C to 65 °C, or 30 °C to 60 °C, including any range therebetween.
  • the synthesis of the ammonia is performed at a temperature of from 25 to 30 °C. In some embodiments, the synthesis of the ammonia is performed at a temperature of from 30 to 50 °C.
  • the synthesis of the ammonia is performed at a pressure of 500 to 2000 mm Hg. In some embodiments, the synthesis is performed at a pressure of 500 to 1000 mm Hg.
  • the synthesis of the ammonia is performed at an ambient temperature. In some embodiments, the synthesis of the ammonia is performed at an ambient pressure. In some embodiments, the synthesis of the ammonia is performed at an ambient pressure and at an ambient temperature.
  • ambient pressure is intended to mean approximately 740 mm Hg to about 780 mm Hg.
  • the electric potential used in the synthesis of the ammonia is in the range of -0.4 V to 0.2 V, -0.3 V to 0.2 V, -0.3 V to 0.2 V, -0.3 V to 0.2 V, -0.1 V to 0.2 V, 0 V to 0.2 V, -0.4 V to 0.1 V, -0.4 V to -0.1 V, or -0.4 V to -0.2 V, including any range therebetween.
  • the synthesis of the ammonia is performed at low electric potential. In some embodiments, the low electric potential avoid hydrogen evolution competing reactions.
  • the rate of ammonia production can be increased by increasing the electric potential.
  • the synthesis of ammonia is characterized by a faradaic efficiency in the range of 1% to 30%, 1% to 25%, 1% to 20%, 1% to 15%, 1% to 10%, 3% to 30%, 5% to 30%, 5% to 25%, 5% to 20%, 5% to 15%, or 5% to 10%, including any range therebetween.
  • the synthesis of the ammonia is characterized by a faradaic efficiency of at least 1% wherein the electric potential is 0.023 V. In some embodiments, the synthesis of the ammonia is characterized by a faradaic efficiency of at least 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, or 25%, wherein the electric potential is 0.023 V.
  • the synthesis of the ammonia is characterized by a faradaic efficiency of at least 1% wherein the electric potential is 0.123 V. In some embodiments, the synthesis of the ammonia is characterized by a faradaic efficiency of at least 2% wherein the electric potential is 0.123 V. In some embodiments, the synthesis of the ammonia is characterized by a faradaic efficiency of at least 3% wherein the electric potential is 0.123 V. In some embodiments, the synthesis of the ammonia is characterized by a faradaic efficiency of at least 4% wherein the electric potential is 0.123 V. In some embodiments, the synthesis of the ammonia is characterized by a faradaic efficiency of at least 5% wherein the electric potential is 0.123 V.
  • the synthesis of the ammonia is characterized by a rate of ammonia production is in the range of 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 5 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 10 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 1 ⁇ 10 -10 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 10 ⁇ 10 -10 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 10 ⁇ 10 -10 mol s -1 cm -2 to 1 ⁇ 10 -7 mol s -1 cm -2 , 1 ⁇ 10 -11 mol s -1 cm -2 to 1 ⁇ 10 -8 mol s -1 cm -2
  • compositions comprising, “comprising”, “includes”, “including”, “having” and their conjugates mean “including but not limited to”.
  • Consisting of means “including and limited to”.
  • Consisting essentially of means that the composition, method or structure may include additional ingredients, steps and/or parts, but only if the additional ingredients, steps and/or parts do not materially alter the basic and novel characteristics of the claimed composition, method or structure.
  • a compound or “at least one compound” may include a plurality of compounds, including mixtures thereof.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • method refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of the chemical, and electrochemical arts.
  • Ruthenium platinum black normally Pt 50%, Ru 50% (atomic wt%), HiSPEC 6000 was purchased from Alfa Aesar.
  • Vulcan XC-72 was procured from Cabot.
  • Potassium hydroxide, isopropyl alcohol, PTFE (60 wt%) solution and nickel foil were procured from Aldrich.
  • Anionic ionmer was purchased from Hephas Energy Co. Ltd.
  • Toray carbon was purchased from fuel cell store.com tm .
  • RuPt/C slurry was prepared by adding RuPt and Vulcan XC 72 (9:1) into glass vial, to this mixture milli-Q water, isopropyl alcohol (1:1), PTFE solution (5 wt%) and inomer (2 wt%) were added and ultra-sonicated for 15 min.
  • the prepared slurry was brush coated on Toray carbon electrode (1 cm -2 ) and dried at 80 °C under vacuum overnight.
  • the Biologic VSP workstation was used to carry out all electrochemical experiments. Hiden analytic HPR 20 mass spectrometry was used for qualitative analysis of gasses.
  • the electrochemical experiments were performed using three electrode system consisting of RuPt/C as working, nickel foil as counter and mercury mercuric oxide (MMO) reference electrodes. 1.0 M KOH solution was used as electrolyte. The dissolved oxygen in electrode was removed by purging argon gas (99.999% pure) for 15 min. For electrochemical synthesis of ammonia, nitrogen gas (99.999% pure) was purged prior to the experiment.
  • Figure 1A shows linear sweep voltammograms (LSVs) of Vulcan XC 72 modified working electrodes in argon and nitrogen saturated solution. As expected, Vulcan XC-72 carbon did not show any catalytic activity for nitrogen reduction reaction (NRR).
  • NRR nitrogen reduction reaction
  • Figure 1C exhibits LSVs of ruthenium/carbon (Ru/C) towards NRR. From this graph it can be observed that there is no significant change in the onset potential of the reaction under argon and nitrogen saturated solutions. Nevertheless, RuPt/C catalyzed electrode exhibited lower onset potential (ca.0.05V) than platinum carbon (Pt/C, ca.0.025V) and ruthenium carbon (Ru/C, ca.0.1V) electrodes in nitrogen saturated solution which is obviously due to NRR (see Figure 1D ). The observed onset potential of NRR is more positive (i.e. -0.077V vs RHE). At a more negative cell potential, the rate of ammonia formation decreased significantly due to hydrogen reduction reaction and became more dominant than that of NRR.
  • RuPt/C catalyzed electrode exhibited lower onset potential (ca.0.05V) than platinum carbon (Pt/C, ca.0.025V) and ruthenium carbon (Ru/C, ca.0.1V) electrodes in nitrogen saturated solution which is
  • the bifunctionalty of PtRu can also be ascribed to removal of hydrogen from Ru sites through reaction 2: Ru ⁇ H ad + Pt ⁇ H ad ⁇ H 2 + RuPt
  • electrochemical ammonia synthesis was carried out in electrochemical cell consisting of RuPt/C working electrode, nickel foil as counter electrode and MMO (1.0M KOH) as reference electrode in 1.0M KOH solution.
  • the produced gases were bubbled in 1mM H 2 SO 4 trap.
  • the minimum threshold potential is required below which electrochemically it is not possible to produce ammonia:
  • Figure 3A depicts the effect of various applied potentials towards NRR at RuPt/C electrode in the cell configuration described above.
  • All the potentials were measured versus MMO and converted into reversible hydrogen electrode (RHE) by calibration as shown in Figure 3B .
  • the rate of ammonia electrochemically formed and corresponding Faradaic efficiency at different applied potentials are given in Figure 3C and summarized in Table 1.
  • a maximum faradaic efficiency of 13.2% was observed at an applied potential of 0.123 V with rate of ammonia formation of 3.0 ⁇ 10 -10 mols -1 cm -2 .
  • On contrary, at -0.077V maximum amount of ammonia produced (6.37 ⁇ 10 -10 mols -1 cm -2 ) with the Faradic efficiency of 1.1%.
  • ammonia formation rate increased from potential 0.123 to -0.077 V and then decreased.
  • Faradaic efficiency decreased as the applied potential increased. This illustrates that at relatively lower potential nitrogen reduction reaction was predominating which competes with by hydrogen evolution at higher potential.
  • the rate of NRR was measured at 30, 50 and 70 °C as shown in Figure 3D .
  • Electrochemical ammonia formation increases from 30 to 50 °C increasing temperature but slightly decreases at 70 °C.
  • Figure 3E presents the rate of ammonia formation and Faradaic efficiency at various temperatures.
  • Dissolved ammonia tests using Nessler reagent confirmed the presence of ammonia in the electrolyte, which is formed in the course of electrochemical nitrogen reduction.
  • the solubility of ammonia in electrolyte significantly decreases from 3 ⁇ 10 -10 mols -1 cm -2 to 9 ⁇ 10 -11 mols -1 cm -2 .
  • the concentration of ammonia in alkaline solution decreases as the temperature increases, for instance, ammonia solubility was decreased from 39.54 g/Liter to 19.71 g/Liter when temperature was raised from 50 to 70 °C.
  • RuPt/C was used as catalyst for electrochemical synthesis ammonia using water and nitrogen at ambient pressure and lower temperature.
  • the linear sweep voltametric experiments of Ru/C, Pt/C and RuPt/C clearly depicted that the latter showed superior nitrogen reduction reaction activity.
  • the high rate of ammonia formation was due to synergistic effect of RuPt alloy.
  • Both temperature and applied potential have significant influence on the rate of ammonia formation.
  • the present catalyst showed better stability and specificity towards nitrogen reduction reaction to form ammonia.
  • Iron nitrate nonahydrate was purchased from Strem Chemicals.
  • Vulcan XC-72 was procured from Cabot. Potassium hydroxide, isopropyl alcohol, concentrated ammonia solution (28 wt.%), titanium dioxide (325 mesh anatase) and nickel foil were procured from Aldrich.
  • Fe 2 O 3 /TiO 2 /C ink was prepared by mixing the catalyst, Vulcan XC-72 carbon and Nafion ® (84, 8 and 8 wt.%, respectively) in a glass vial, with water and isopropyl alcohol (1:1 v/v) added to the mixture.
  • This slurry was stirred overnight on a magnetic stirrer, brush-coated onto nickel foam and dried at 90 °C for 2 h in an air-convection oven.
  • the commercials catalysts such as titanium powder, titanium nanoparticles, titanium hydride were purchased from Strem Chemicals. Platinum black, palladium black and ruthenium platinum alloy were procured from Alfa Aesar.
  • the anionic membranes (quaternary ammonium polysulfone, thickness 40 ⁇ m) were bought from Hephas Energy Co. Ltd.
  • the resulting thick mass was transferred into a hydrothermal bomb, and an appropriate amount of water was added until 70% of the total volume of the hydrothermal bomb was filled with liquid. Finally, the hydrothermal reaction was carried out at 100 °C for 15 hours. After that, the reaction mixture was cooled down to room temperature. The final product was filtered and washed extensively with Milli-Q ® water to remove the ammonium nitrate formed during the reaction (complete removal of ammonium nitrate was confirmed by Nessler's reagent). The obtained product was dried at 80 °C overnight as previously described.
  • Fe 3+ ions were precipitated as hydrated iron(III) oxide under the alkaline condition, and the obtained product was further transformed into FeOOH, as shown in Reactions (1) and (2), respectively. Under heating, the Fe(III)OOH was converted into Fe 2 O 3 , as given in Reaction (3).
  • a BioLogic VSP potentiostat was used in all electrochemical experiments.
  • a Hiden Analytical HPR-20 mass spectrometer was used for qualitative analysis of gases.
  • the electrochemical experiments were performed using a three-electrode system consisting of Fe 2 O 3 /TiO 2 /C-coated nickel foam as a working electrode, nickel foil as a counter electrode and mercury/mercury-oxide (MMO, 1.0 M KOH) as a reference electrode.
  • MMO mercury/mercury-oxide
  • a 1.0 M KOH solution was used as an electrolyte in all experiments. All the potentials were measured versus a mercury/mercury-oxide reference electrode and converted by calibration method into a potential versus reversible hydrogen electrode (RHE).
  • nickel foil was used as the working electrode (even at high overpotentials) there was no detectable ammonia oxidation. Therefore, pure nickel foil was used as a counter electrode in the present work without a risk of possible consumption of electrochemically produced ammonia.
  • the dissolved oxygen was removed from the electrolyte by purging with argon gas (99.999% pure) for 20 min.
  • high-purity nitrogen gas (99.999% pure) was purged prior to the experiment for 20 min.
  • the acid trap and the alkaline electrolyte solutions were used for the quantification of electrochemically produced ammonia by adding Nessler's reagent and measuring the absorbance at 420 nm ( Figure 2A ).
  • the exact ammonia concentration was determined by linear regression (5-point calibration curve).
  • the final amount of ammonia obtained from NRR was calculated by adding the ammonia content found in the acid trap to that present in the alkaline electrolyte.
  • Fe 2 O 3 powder was synthesized by using the aforementioned synthesis protocol in ammonia solution.
  • the 2-theta peaks at 25.27, 37.77, 48.01, 53.88, 55.03, 62.66, 68.78, 70.30 and 75.04° correspond to the (101), (004), (200), (105), (211), (204), (116), (220) and (215) planes of an anatase crystalline TiO 2 phase ( Figure 1B ).
  • FeOOH particles were formed during the addition of ammonia solution to the suspension of TiO 2 support and were then converted to a crystalline Fe 2 O 3 phase during the hydrothermal treatment.
  • Figs. 7C-D show SEM and EDX mapping of the Fe 2 O 3 /TiO 2 composite.
  • the SEM image shows the aggregate of Fe 2 O 3 particles on the surface of the underlying TiO 2 (40 microns).
  • Fe 2 O 3 /TiO 2 composites contain 26.5 and 10.8 atomic % of Fe and Ti, respectively.
  • the optimal ratio of starting materials i.e. 6 mmol Fe(NO 3 ) 3 and 2 mmol TiO 2
  • the optimal ratio of starting materials is optimized by determining the highest ammonia formation ratio for different amounts of iron(III) nitrate and titanium dioxide used for the synthesis of the catalyst, as shown in Figure S5.
  • the atomic ratios of Fe, Ti and O were theoretically calculated to be 28, 9.5 and 62%, respectively. These values are very close to the ratio found by EDX analysis (as given in Figure 8 ), proving that the optimal composition of the catalyst was used in this work.
  • LSVs Linear sweep voltammograms of the nickel-foam working electrodes in a 1.0 M KOH-saturated solution are shown in Figure 9A .
  • LSVs Linear sweep voltammograms
  • bare nickel foam was used as a working electrode in either argon or nitrogen-saturated electrolytes. Therefore, nickel foam can be used as an excellent substrate, due to its high porosity and electrochemical inertness towards NRR in the potential window applied.
  • the TiO 2 /C electrode did not show any NRR in the presence of the N 2 -saturated electrolyte, as shown in Figure 9B .
  • the Fe 2 O 3 -coated nickel-foam electrode (loading: 15 mg cm -2 ) in the nitrogen-saturated 1.0 M KOH solution exhibited an increase in the reduction current without any significant change in onset potential (-0.183 V vs. RHE), in contrast to the argon-saturated electrolyte. Nevertheless, the rate of ammonia formation on the Fe 2 O 3 -coated Ni-foam electrode was 2 ⁇ 10 -10 mol s -1 cm -2 at an applied potential of -0.277 V vs. RHE. The onset potential of HER recorded in the argon-saturated solution on the Fe 2 O 3 /TiO 2 composite electrode was -0.2 V.
  • the molar ratio between Fe 2 O 3 and TiO 2 was 60% and 40%, respectively, as calculated from the starting amounts of iron(III) nitrate and titanium dioxide.
  • the rate of ammonia formation was found to be almost one order of magnitude higher on the TiO 2 -supported catalyst (1.2 ⁇ 10 -9 mol s -1 cm -2 ) compared to an unsupported iron-oxide catalyst (2.0 ⁇ 10 -10 mol s -1 cm -2 ) at an applied potential of -0.277 V vs. RHE.
  • the rate further increased to 1.9 ⁇ 10 -9 mol s -1 cm -2 with the same loading when 10 wt.% of Vulcan-XC carbon was added to improve the electron charge transfer process between the catalyst and the current collector.
  • TiO 2-x x ⁇ 0.01
  • TiO 2-x x ⁇ 0.01
  • This oxygen deficiency is due to the presence in both forms of a small amount of Ti 3+ impurity in the titania crystalline structure.
  • Hirakawa et al. have used commercial anatase as a photocatalyst for ammonia synthesis from water and nitrogen at atmospheric pressure and room temperature. The photocatalytic activity of the TiO 2 was attributed to the Ti 3+ surface species serving as active sites for nitrogen reduction.
  • the XRD of the obtained product clearly showed the existence of a magnetite phase along with excess Fe 2 O 3 and elemental iron.
  • the possible underlying mechanism for the synergic behavior between Fe 2 O 3 and TiO 2 regarding the NRR could be understood as based on the interfacial intervalence charge transfer between Ti 4+ (from TiO 2 ) and the Fe 2+ species that are formed during the partial electroreduction of the iron (III) oxide catalyst. Such phenomena were reported earlier for various Fe-Ti containing minerals. This kind of electron exchange might result in regeneration of the Fe 2 O 3 catalyst and the concomitant formation of Ti 3+ species that present additional active sites for NRR, as mentioned before.
  • Figures 11A and 11B depict the influence of selected applied potentials on NRR at the Fe 2 O 3 /TiO 2 catalysts.
  • the various ammonia electrochemical formation rates and their corresponding faradaic efficiencies are given in Figure 11C and summarized in Table 3.
  • a maximum faradaic efficiency of 21% was observed at a low applied potential of 0.023 V with a slow ammonia formation rate of 1.5 ⁇ 10 -10 mol s -1 cm -2 .
  • the maximum rate of ammonia formation of 6.3 ⁇ 10 -9 mol s -1 cm -2 was attained at a high applied potential of -0.577 V with a faradaic efficiency of 1.8%.
  • FIG. 13A shows chronoamperometric curves of the Fe 2 O 3 /TiO 2 /C composite painted on nickel-foam electrodes in 1.0 M KOH solutions saturated with nitrogen and air at a potential of -0.277 V.
  • air-saturated electrolyte yielded a rate of 1.7 ⁇ 10 -9 mol s -1 cm -2 , a value comparable to the ammonia formation rate determined in nitrogen-saturated electrolyte (i.e. 1.9 ⁇ 10 -9 mol s -1 cm -2 at -0.277 V).
  • m/z mass-to-charge ratios
  • Fe 2 O 3 /TiO 2 /C was used as a catalyst for electrochemical synthesis of ammonia, using water and nitrogen at ambient pressure and room temperature.
  • the chronoamperometric and linear sweep voltammetric experiments on the Fe 2 O 3 /TiO 2 /C clearly confirmed that Fe 2 O 3 together with TiO 2 shows better nitrogen reduction reaction activity than Fe 2 O 3 alone.
  • the high rate of ammonia formation was due to the synergistic effect of iron oxide/TiO 2 .
  • Applied temperatures and electrode potentials showed a significant impact on the rate of ammonia formation.
  • the present catalyst showed remarkable activity and good stability for NRR, even when air was used as the nitrogen source.
  • Fe 2 O 3 /TiO 2 /C ink was prepared by mixing the catalyst, Vulcan XC-72 carbon and Nafion ® (84, 8 and 8 wt.%, respectively) in a glass vial, with water and isopropyl alcohol (1:1 v/v) added to the mixture. This slurry was stirred overnight on a magnetic stirrer, brush-coated onto nickel foam and dried at 90 °C for 2 h in an air-convection oven.
  • Nessler's reagent method is very simple and fast way to detect/determine the presence of ammonia. It is ready to use reagent (0.09 mol/L solution of potassium tetraiodomercurate(II) (K 2 [HgI 4 ]) in 2.5 mol/L potassium hydroxide) prepared from aqueous solution of mercuric iodide and potassium iodide. This reagent reacts with ammonia and gives yellow color due to formation of iodide of Millon's base as shown in below reaction. NH 4 + + 2 [HgI 4 ] 2- + 4 OH - ⁇ HgO ⁇ Hg(NH 2 )I (iodide of Millon's base) + 7 I - + 3 H 2 O
  • the argon saturated solution is transferred into a Teflon lined autoclave heated up to 200 °C for 9.5h. Once the mixture is cooled to room temperature, the ethylene glycol was separated by centrifugation and the crude solid product is washed 5 times with absolute ethanol. Following the washing cycles, the Ru x Sn y /C samples were dried in the vacuum oven at 60 °C for 1h with an additional drying cycle at 80 °C and atmospheric pressure. Ru/C is synthesized in the same way as Ru x Sn y /C while the Sn/C required additional reduction step in hydrogen-argon atmosphere (20%-80% v/v) at 400 °C for 2h to reduce the formed SnO 2 /C nanoparticles into its metallic Sn form.
  • Figure 17 presents the STEM images of RuSn/C samples.
  • the image shows spherical RuSn nanoparticles, with a size distribution ranging from 3-15 nm, are attached to the surface of the carbon support used in the synthesis of the catalyst.
  • Linear Sweep Voltammetry (LSV)and chronoamperometry have been used to examine the electrocatalytic properties of Ru x Sn y catalyst.
  • Figure 18A presents the LSV of the Ru/C and RuSn/C (50% each metal) recorded in nitrogen saturated 0.1M Na 2 SO 4 .
  • the significant shift in an HER (and concomitant NRR) overpotential of ca. 100 mV has been noticed as expected for the alloys that contain the HER "resistant" elements such as Sn.
  • the total catalyst loading, i.e. RuSn/C along with Nafion binder, in both cases was similar (2.2 mg for RuSn/C and 2.4 mg for Ru/C), significant decrease in current can be noticed. This can be ascribed to impeded HER on this type of catalysts.
  • Ammonia formation rates and Faradaic efficiencies are calculated from chronoamperometric curves, recorded in a nitrogen saturated atmosphere and a constant potential during the period of 2h.
  • the optimal rate optimization and corresponding Faradaic efficiencies are shown in Figure 18B .
  • the highest ammonia formation rate of 2.25 ⁇ 10 -8 mol s -1 mg -1 was achieved at -200 mV (vs RHE) with Faradaic efficiency of ca. 1%.
  • FIG 2A the appearance of HER (appears negative currents) are delayed by 100 - 200 mV, allowing in RuSn at higher efficiency.
  • Figure 19A presents the LSV of the Ru/C and RuSn/C (50% each metal) recorded in nitrogen saturated 0.1M Na 2 SO 4 .
  • the significant shift in an HER (and concomitant NRR) overpotential of ca. 100 mV has been noticed as expected for the alloys that contain the HER "resistant" elements such as Sn.
  • the total catalyst loading, i.e. RuSn/C along with Nafion binder, in both cases was similar (2.2 mg for RuSn/C and 2.4 mg for Ru/C), significant decrease in current can be noticed. This can be ascribed to impeded HER on this type of catalysts.
  • the best catalyst for electrochemical ammonia synthesis is the synthesized Fe 2 O 3 /TiO 2 /C.
  • the Fe 2 O 3 /TiO 2 /C is a very low cost material, the synthesis method requires soft conditions of temperature and pressure and can be easily upscaled.
  • the rate of ammonia formation depends on the temperature and strength of KOH.
  • the cell temperature up to 50 °C and 5.0 M KOH (as an electrolyte) leads higher yield of ammonia.
  • at room temperature rate of ammonia formed in the order of (4 ⁇ 1) ⁇ 10 -9 on the other hand at 50 °C rate of ammonia formation has been increased up to (1 ⁇ 0.5) ⁇ 10 -8 mol s -1 cm -2 .
  • MEA Membrane electrode assembly
  • cathode electrode catalyst coated Toray carbon 4 cm -2
  • Pt/C coated Toray carbon 4 cm -2 anode
  • alkaline membrane quaternary ammonium polysulfone, 40 ⁇ m thickness
  • cathode side high purity nitrogen (99.999) has been introduced and on the other anode side 1.0 M KOH has been continuously circulated (5 ml/min.) by using peristaltic pump. Above mentioned procedure is followed to determine the quantity of ammonia produced during the electrochemical reaction.
  • the nitrogen reduction reaction catalyst and electrolyte oxidizing catalyst were used as cathode and anode respectively.
  • the known quantity of humidified nitrogen was passed through gas diffusion layer coated with catalyst and 1.0 M KOH electrolyte continuously circulated to the anode by using peristaltic pump.
  • nitrogen gas reduced to ammonia at cathode (as shown in equation 4) and was trapped in 10 mM H 2 SO 4 for the quantification.
  • electrolyte oxidized to oxygen as shown in equation 5. The overall net reaction is given below.
  • Linear sweep voltammogram (LSV) of nickel foil anode-alkaline membrane-Fe 2 O 3 /TiO 2 composite -cathode fuel cell type prototype configuration under nitrogen gas atmosphere is depicts in Figure 21A .
  • This configuration produces very high currents, due to the low ohmic resistance of the electrolyte membrane/separator.
  • the cell consists of detachable plastic vessel and rubber cork.
  • Cathode part of cell is the vessel (bottle or glass) that include:
  • the working electrode (1 on Fig.22 ) that can be a free form and that placed in vessel.
  • the nitrogen gas is purged nearby working electrode (3 on Fig.22 ) by silicon tubing with holes for nitrogen bubbling and immersed in electrolyte; the produced ammonia gas at the working electrode come out in silicon tubing and trapped in diluted acid.
  • Anode part of cell is plastic tube that fit in vessel and include anode (Ni foil).
  • the rate of electrochemical nitrogen reduction reaction of Fe 2 TiO 3 /TiO 2 /C (4.9 cm 2 ) electrodes at 50 °C in two electrode system were found to be 1.05 ⁇ 10 -8 and 1.1 ⁇ 10 -8 mol s -1 cm -2 with faradaic efficiencies 5.1 and 4.3.
  • Ammonia dissolves in aqueous solution ( ⁇ 28 wt%), keeping this point in mind above electrochemical cell has been developed which can work with minimal quantity of electrolyte. As a result electrochemically generated ammonia saturates quickly in electrolyte and comes out from the cell and collects in acid trap. On the other hand, nitrogen is passing through the catalyst coated carbon felt; as a result most of the active sites are utilized for the electrochemical nitrogen reduction reaction.
  • the ammonia formation rate is higher at 50 °C than RT. As KOH electrolyte concentration increased, the rate of ammonia formation increased. This could be due to catalyst active sites available for nitrogen reduction reaction than hydrogen evolution reaction. More importantly, Fe 2 TiO 3 /TiO 2 /C catalyst showed sataisfactory stability as shown in Figure 26 .

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Claims (11)

  1. Composition comprenant un premier composant métallique et un second composant métallique caractérisée par un rapport molaire dudit premier composant métallique audit second composant métallique dans la plage de 1:9 à 9:1, dans laquelle :
    (i) au moins une surface dudit second composant métallique est recouverte dudit premier composant métallique ;
    (ii) le premier composant métallique comprend Fe2O3 ou Fe3O4 ou Fe2O3FeO et dans laquelle ledit second composant métallique comprend TiO2, et
    (iii) ladite composition est sous la forme de particules.
  2. Composition selon la revendication 1, dans laquelle lesdites particules ont une taille dans la plage de 1 nm à 50 µm, déterminée par imagerie STEM.
  3. Composition selon l'une quelconque des revendications 1 et 2, comprenant en outre un substrat, dans laquelle ledit premier composant métallique et ledit second composant métallique sont déposés sur au moins une surface dudit substrat, dans laquelle ledit substrat est facultativement choisi dans le groupe constitué de : noir de carbone, charbon actif, graphite, nanotube de carbone, et toute combinaison de ceux-ci, en outre facultativement dans laquelle ledit noir de carbone est choisi dans le groupe constitué de : nanotube de carbone et graphène.
  4. Composition selon la revendication 3, dans laquelle ledit substrat est présent à une concentration de 5 % à 50 %, en poids total de ladite composition.
  5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle ladite composition est un catalyseur.
  6. Composition selon la revendication 5, dans laquelle ledit catalyseur est caractérisé par une activité électrocatalytique en vue d'une réduction d'azote.
  7. Cellule électrochimique caractérisée en ce qu'elle a une cathode comprenant le catalyseur selon la revendication 5.
  8. Cellule électrochimique selon la revendication 7, comprenant un électrolyte alcalin, dans laquelle la cellule électrochimique est configurée pour une synthèse électrochimique d'ammoniac.
  9. Cellule électrochimique selon la revendication 7, comprenant en outre :
    un conteneur de cellule d'électrolyse comprenant une entrée et une sortie ;
    un distributeur, ledit distributeur étant en communication fluidique avec ladite cathode et ladite entrée ; et
    une anode, dans laquelle :
    (i) lesdites anode et cathode sont espacées l'une de l'autre à l'intérieur du conteneur ;
    (ii) ladite anode est en communication électrique avec ladite cathode ;
    (iii) la dimension la plus grande de ladite anode et de ladite cathode est définie par des dimensions en coupe transversale dudit conteneur de cellule d'électrolyse ; et
    (iv) ladite cathode est au moins 50 fois plus épaisse que ladite anode.
  10. Cellule électrochimique selon la revendication 9, dans laquelle l'un quelconque parmi : (i) ledit conteneur est configuré pour permettre à un gaz d'azote d'entrer à travers ladite entrée et d'entrer en contact avec ledit distributeur ; (ii) ledit distributeur est configuré pour distribuer uniformément ledit gaz sur une surface de ladite cathode ; (iii) dans laquelle ladite cathode, ladite anode ou les deux, sont au moins partiellement poreuses ; (iv) dans laquelle ledit conteneur est configuré pour permettre à un gaz d'azote d'entrer dans celui-ci et d'entrer en contact avec ladite cathode ; (v) ladite cellule électrochimique est configurée pour synthétiser de l'ammoniac à un taux de 1 × 10-11 mole s-1cm-2 à 1 × 10-7 mole s-1cm-2 à 1 atm N2 ; et (ii) dans laquelle le gaz restant est dirigé via ladite sortie dans une chambre de collecte, facultativement dans laquelle ladite chambre de collecte est un piège à acide.
  11. Procédé de synthèse d'ammoniac, le procédé étant caractérisé par une efficacité faradique dans la plage de 1 % à 30 %, et comprenant les étapes consistant à :
    (i) mettre en contact un gaz d'azote avec la cathode de la cellule électrochimique selon la revendication 10, et
    (ii) appliquer un potentiel électrique à l'anode et à la cathode, en obtenant ainsi ledit ammoniac, facultativement dans lequel :
    ladite synthèse est réalisée à une température de 20 °C à 80 °C ; ou le taux de production d'ammoniac est dans la plage de 1 × 10-11 mole s-1cm-2 à 1 × 10-7 mole s-1cm-2.
EP19781678.8A 2018-04-02 2019-04-02 Électro-catalyseurs, leur préparation,et leur utilisation pour la synthèse de l'ammoniac Active EP3774027B1 (fr)

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WO2022060920A2 (fr) * 2020-09-16 2022-03-24 The Board Of Trustees Of The University Of Illinois Dispositif et procédés de production d'ammoniac et de nitrates dans des conditions ambiantes
CN113073354A (zh) * 2021-03-25 2021-07-06 辽宁大学 铋&钌双金属自支撑电催化材料及其制备方法和在氮气还原中的应用
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